Color photographic printing paper

ABSTRACT

A COLOR PHOTOGRAPHIC PRINTING PAPER CONTAINING AN ULTRAVIOLET ABSORBENT AND A FLUORESCENT BRIGHTENING AGENT REPRESENTED BY THE FORMULA   X-((4-R1-S-TRIAZIN-1,6-YLENE)-N(-R0)-(3-(M-O3S-)-1,4-   PHENYLENE)-CH=CH-(2-(M-O3S-)-1,4-PHENYLENE)-N(-R0)-(4-R1-   S-TRIAZIN-2,6-YLENE)-N(-R2)-Y-N(-R2))N-X, AND X-((4-R1-   S-TRIAZIN-2,6-YLENE)-N(-R0)-(3-(M-O3S-)-1,4-PHENYLENE)-CH=   CH-(2-(M-O3S-)-1,4-PHENYLENE)-N(-R0)-(4-R1-S-TRIAZIN-2,6-   YLENE)-N(-R2)-Y-(Z)-Y-N(-R2))N-X

# d States Patent 01 3,676,139 Patented July 11, 1972 7 The portion ofthe term of the patent subsequent to Oct. 26, 1988, has been disclaimedInt. Cl. G03c 1/92, 1/84 U.S. Cl. 96-82 9 Claims ABSTRACT OF THEDISCLOSURE A color photographic printing paper containing an ultravioletabsorbent and a fluorescent brightening agent represented by theformulas the solution to dye the gelatin with the fluorescentbrightening agent. However, this method has the disadvantage that it isdiflicult to dye selectively a necessary layer with a fluorescentbrightening agent. In addition, an additional processing bath containingthe fluorescent brightening agent is required.

There has also been proposed a direct-addition method, in which afluorescent brightening agent is added directly as an aqueous solution01' an organic solvent solution thereof to an emulsion or a dispersionfor a photographic silver halide emulsion layer or to a supplementallayer. An indirect methd has been proposed, in which a fluorescentbrightening agent is dissolved in a solvent having a high boiling point(or a mixture of a high boiling solvent and an auxiliary solvent), thesolution dispersed in an aqueous gelatin solution, and this dispersionadded to a photographic light-sensitive emulsion.

However, since the known fluorescent brightening agents are usually lowmolecular weight compounds, when they are incorporated in photographicemulsion layers or sup- The present invention relates to a colorphotographic printing paper containing a fluorescent brightening agentand an ultraviolet absorbent. More particularly, the invention relatesto a color photographic printing paper having a photographic layercontaining a watersoluble, fluorescent brightening agent having ananti-diffusion property to fluorescent-whitening and an ultravioletabsorbent to prevent fading and stains caused by ultraviolet rays.

The whitening of photographic printing papers has previously beenaccomplished by a method comprising adding a fluorescent brighteningagent to the baryta layer of a baryta paper. However, even if abaryta-coated paper is whitened by the aforesaid conventional method,the whitening effect is lost in color photographic printing paper, sincesuch papers must also contain a compound capable of absorbingultraviolet rays, such as, ultraviolet absorbent and a coupler.

Therefore, various suggestions have been made to supplement thewhitening effect thus lost. For example, there has been proposed amethod in which a water-soluble fluorescent brightening agent isincorporated in a processing solution and a gelatin-containing layer isprocessed by plemental layers, the greater part of the fluorescentbrighteningagents is diffused out during processing and washing, wherebythe whitening eflect thereof is weakened.

Various proposals have been made to avoid the above disadvantages of theprior art processes. For instance, there has been proposed a method inwhich a substituent capable of improving dyability is introduced intogelatin. For example, polyvinyl pyrrolidone (Japanese Pat. No.7127(1959)) and poly-N-vinyl-5-methyl-3-oxazolidinone (Japanese Pat. No.22,065 (1964) each being capable of being readily dyed by a fluorescentbrightening agent, have been dispersed in an aqueous gelatin solutionand then dyed by a fluorescent brightening agent. However, even byemploying such methods, the diffusion of the fluorescent brighteningagent employed has yet to be sufi'iciently prevented and the whiteningeffect of the agent is still considerably degraded during photographicprocessing and washing.

The inventors have previously found that as disclosed in their U.S.application Ser. No. 720,344, filed Apr. 10, 1968 now Pat. No.3,556,081, the aforesaid disadvantages are overcome to the same extentby using, as the fluorescent brightening agent a compound having arepeating unit represented by one of the following general formulas:

l 1 n (II) wherein R and R each represents a hydrogen atom, an alkylgroup having 1-8 carbon atoms, an aryl group having 6-12 carbon atoms, ahydroxyalkyl group having 2-4 carbon atoms, or a substituted derivativethereof, a sulfoalkyl group having 1-4 carbon atoms, or an alkali metalsalt or ammonium salt thereof; R represents a halogen atom, OR, SR,

wherein R and R each represents a hydrogen atom, an alkyl group having1-12 carbon atoms, a hydroxyalkyl group having 1-12 carbon atoms, asulfoalkyl group (or an alkali metal salt or an ammonium salt thereof) acarboxyalkyl group (or an alkali metal salt or an ammonium saltthereof), or an alkyl group, an aryl group having 6-18 carbon atoms, ahydroxy-, carboxyor sulfonic acidderivative thereof, or an alkali metalsalt or an ammonium salt thereof, a cycloalkyl group having 2-10 carbonatoms, or a substituted cycloalkyl group; and wherein A represents analkylene group having 4-5 carbon atoms or an alkylene group containing aheterocyclic atom or a heterocyclic atomic group; Y represents analkylene group having 2-10 carbon atoms, a substituted alkylene grouphaving 2-10 carbon atoms, an allylene group having 6-18 carbon atoms ora substituted allylene group having 6-18 carbon atoms; Z represents adivalent heterocyclic atom or atomic group; M represents an alkali metalatom or NH X represents OH, Cl or NH m is 0 or 1 and n is to 120. Thatis, the fluorescent brightening agent is less difiused out duringphotographic processing or washing when incorporated in a photographicemulsion layer or a supplemental layer. Further, it has been found thatthis is resistant to staining when exposed to ultraviolet rays.Furthermore, these fluorescent brightening agents have been found to beexcellent in fluorescent intensity and wave length.

It is also known to incorporate an ultraviolet absorbent in thephotographic emulsion layer or an upper layer applied on thatphotographic emulsion layer for improving the fade-resistance of colorimages. The known ultraviolet absorbents are those absorbing ultravioletrays having wave lengths of 300-400 me. It is also known that aultraviolet absorbent capable of absorbing ultraviolet rays having wavelengths as long as possible is more effectively employed.

However, when the absorption edge of known ultraviolet absorbentsextends across 400 me, the ultraviolet absorbent becomes yellow incolor, and thus influences adversely the whiteness of the printingpaper.

It is therefore, an object of this invention to provide a colorphotographic printing paper wherein the above coloration, resulting fromthe use of an ultraviolent absorbent, is substantially avoided.

It is a further object of this invention to provide a color photographicprinting paper which has been whitened by a fluorescent brighteningagent, wherein fading of the color upon exposure to light is reduced bythe addition of an ultraviolet absorbent, without adversely affectingthe whiteness thereof.

A further object of this invention is the provision of a colorphotographic printing paper containing an ultraviolet absorbent and afluorescent whitening agent which is not subject to the aforesaiddisadvantages.

The aforesaid objects of the present invention can be achieved byincorporating a fluorescent brightening agent having at least onerepeating unit represented by the general Formula I or II in at leastone photographic layer of a color photographic printing paper, saidlayer containing an ultraviolet absorbent, and photographic layers 4present at the side of said photographic layer containing theultraviolet absorbent and opposite to the support side of the paper.

For example, in one embodiment of a color photographic printing paper,there are provided on a support, a baryta layer, a blue-sensitiveemulsion layer containing a yellow coupler, an intermediate layer, agreen-sensitive emulsion layer containing a magenta coupler, anintermediate layer, a red-sensitive emulsion layer containing a cyancoupler, and a protective layer in that order. The ultraviolet absorbentis incorporated in the intermediate layer between the cyancouplercontaining emulsion layer and the magenta coupler-containingemulsion layer and the fluorescent brightening agent is incorporated inthe protective layer.

The fluorescent brightening agent used in the present invention is ahigh molecular weight compound having the repeating unit of the generalFormula I or II as mentioned above. The ultraviolet absorbent used inthis invention may be, for instance,

(1) A benzotriazole derivative represented by the following generalformula:

(III) wherein R R and R each represents a hydrogen atom, a halogen atom,a nitro group, an alkyl group, an aromatic group, or a heterocyclicring;

(2) A benzophenone derivative represented by general Formula IV I R2" OHwherein R" represents a hydrogen atom, an alkyl group, a cycloalkylgroup, an aralkyl group, or an aryl group; R represents an aryl group ora pyridyl group; and Q represents an imino group, a thiazole derivative,a cinnamic acid ester derivative, an oxazole derivative, an imidazolederivative, an oxadiazole derivative, thiadiazole derivative, athiophene, benzalazine derivative, or a bishydroxyarylamide compound.

The ultraviolet absorbent may be incorporated in the coating compositionfor photographic layer as (1) an emulsified dispersion in an aqueousgelatin solution, (2) a solution thereof in a high boiling solvent or amixed solvent containing a high boiling solvent and a low boilingsolvent or (3) an aqueous alkaline solution thereof.

The high molecular weight fluorescent brightening agents employed in thepresent invention and methods of preparing them are described completelyin copending US. application Ser. No. 720,344, filed Apr. 10, 1968.

As set forth therein, the high molecular Weight compounds having therepeating unit represented by aforesaid general Formula I or II aregenerally prepared by dissolving or dispersing in a solvent, such aswater or dimethylformamide, one mol of an S-triazine-stilbene derivativehaving the general formula R1 in (III) wherein X represents a halogenatom or an alkoxy group having 1-4 carbon atoms and R R and M are asindicated above, and about one mol of a diamino compound represented bygeneral Formula IV or V as follows:

ELY-13 (III) Illa Illa HNY-(Z)m-YNH (V) wherein R Y, Z, and m are asindicated above, reacting this mixture at a temperature of from about 50to 150 C. with the addition of 2-2.4 mols of an aqueous sodium hydroxidesolution. In addition high molecular weight compounds of this inventionmay be prepared by other methods and may be employed in this invention.

The bis-S-triazine-stilbene derivative described by general Formula IIImay be prepared by conventional methods, as shown in The Journal of theSociety of Organic Chemistry, Japan, vol. 20, 64 (1962).

For example, the derivative may be prepared by reacting 2 mols ofcyanuric chloride with one mole .of a derivative of4,4'-diaminostilbene-2,2-disulfonate represented by the general formulal wherein R and M are as set forth above, at a temperature of about C.to C. The compound thus obtained is reacted with 2 mols of anucleophilic agent illustrated by the formula HR wherein R is as setforth above, at a temperature of from about 0 to 20 C.

Some examples of R R, Y, and Z' in the repeating unit (I) or (H) of thehigh molecular weight compound of this invention are as follows: R and Rmay be, for example: H, -CH 2 5 3 T, 2 a)2 -CH CH OH, -CH CH CH OH, CHCH 0CH CH CH OCH --CH -SO M' (where M represents H, Na, K or NH (CH SOM, -(CH SO M', and the like.

R may be for example:

COOM

sonvr' on 503M, COOM' 30 (where M=H, Na, K or NH and P=1, 2, 3 or 4 Asexamples of Y may be mentioned:

(Where M'=H, Na, K or NH Z may be exemplified QCH=CH- by O, S, and S0Typical examples of compounds included in general 03M a Formulas I or IIwhich may be used in this invention 5 are as follows:

SOaNH4 N N SOaNHa It will, of course, be understood, that the number ofrepeating units (represented by n) set forth in the foregoing examplesmay vary to some extent, the narration in some instances being up toabout :20 repeating units.

These compounds may generally be prepared by the methods describedabove, but an example will be given in detail for Compound 1.

A solution of 14.7 parts by weight of cyanuric chloride in 80 parts ofacetone is dispersed in a slurry of 240 parts by Weight of ice water,and the dispersion is maintained at about 0-3 C. To the dispersion thereis added dropwise 16.5 parts of sodium4,4'-diaminostilbene-2,2'-disulfonate as a aqueous solution. During theaddition, hydrochloric acid is formed in the system, and an aqueoussolution of sodium carbonate is added dropwise (4.2 parts by weightsodium carbonate and 50 parts by weight water) so that the pH of thesystem is in the range of 4-5. The system is, thereafter, stirred forabout 30 minutes at about 0-5 0., and 7.5 parts of aniline is furtheradded to the reaction mixture. Thereafter, the temperature of the systemis increased to 20 C. and an aqueous solution of sodium carbonate (4.2parts by weight sodium carbonate and 60 parts by weight water) is addedgradually to the system.

After conducting the reaction for about 3 hours at the same temperature,2.4 parts by weight of ethylenediamine is added to the reaction mixture,and the reaction temperature is increased to 100 C. The reaction mixtureis stirred for 2 hours at 100 C. Upon filtering the reaction mixtureafter cooling, Compound 1 is obtained.

The compound thus obtained is soluble in a dimethylformamide-water 1:1solvent, and the intrinsic viscosity of the compound in the same solventis 0.32 at 30.0 C.

Likewise, typical examples of ultraviolet absorbents. which may be usedin the present invention are as follows:

CAHB (t) o dnzomon Proportions of high molecular weightfluoroscent'brightening agent which may be employed in the printingpapers brightening agent of this invention range from 05-10 mg./ 100 cm.and those of the ultraviolet absorbent range from 2-20 mg./100 cm. v p

Almost all conventionally known fluorescent brightening agents aresimultaneously ultraviolet absorbents. The fluorescent brightening agentmay be added to the system by either the direct or the'indirect methodas set forth above. I i

When known fluorescent brightening agents are added to an uppermostlayer of a photographic light sensitive color printing paper by theindirect method,-that1ayer frequently becomes subject to damage byexternal impact or friction. vFurther, the layer may become sticky,particularly when mounted in an album as a result of solvent action.Therefore, when such conventional fluorescent brightening agents areemployed, they must be incorporated in a photographic layer other thanthe uppermost layer.

However, when the fluorescent brightening agents of this invention areemployed, it is possible to incorporate them in the uppermost layerwithout incurring such disadvantages. Hence the fluorescent brighteningagents of this invention may be incorporated in the uppermost layer tobe effectively utilized as an ultraviolet absorbent.

, Of course, it will be understood that the high molecular weightcompound of this invention may be incorporatedin any layer to effectultraviolet preventing and fluorescent brightening action.

The term photographic emulsion in this application is defined to meanthe usual gelatino silver halide light sensitive emulsions, butsynthetic resins such as polyvinyl alcohol and polyvinyl acetate may beeffectively employed as protective colloids for the photographicemulsion, in addition to gelatin, in this invention. I

In the present invention, the order ofthe photographic layers, as wellas the number of the layers, may be varied as is well known in the art.Moreover, the "ultraviolet absorbent of this invention may beincorporated in any layer except the protective, or uppermostlayei'.Further,

the fluorescent brightening agents of this invention may be agent ofthis invention was incorporated in the uppermost incorporated either inthe layer containing the ultraviolet layer, the use of a whiteningprocedure for the baryta absorbent or in a layer positioned at the sideof the ultralayer was unnecessary.

violet absorbent-containing layer opposite to the side of EXAMPLE 2support. To a bar a-coated a er was a lied a blue-sensitive mventlon {mybe lnuitrated i the fOHPWIiIg typl' silver iodob i omide em ul ion contai r l ing 3,5-dicarboxy-acal examples whlch .exemphfy vanous fombmatlonsof (4-stearoylamidobenzoyl) acetanilide as a yellow coupler.

the water'soluble hlgh molecular welght fluorescent The coupler wasadded as an aqueous alkaline solution brightening agent and theultraviolet absorbent, although the reof. Thereafter a ecu-sensitivesilver chlorobromrde t will be understood that the rnventlon shall notbe 11memulsion containing f (3 sulfo 4 phenoxy) 3 stearoy1 5 therebypyrazolone as a magenta coupler was applied to the blue- EXAMPLE 1sensitive layer. An ultraviolet absorbent, one of the Com- Compound 1,supra, was employed as the high molecular PP -23, Supra, Was {lispersedy emulsification in weight fluorescent brightening agent, and the effectthereof flf P f and the fllspersion Was added to a Was measured A colorphotographic paper con. sensltlve Sliver Chlorobl'omlde emulsion togtherN- sisting of a support, a baryta paper, a blue-sensitive emul- Y Y- 'Pp as y sion layer containing 3,5-dicarboxy-a-(4-stearoylamidop f f heresultmg emulsron was applied to the benzoyl) acetanilide as the yellowcoupler, an intermediate green'sensltlve emulslon f y fills y there waslayer, a green-sensitive emulsion layer containing 1,3-sulfofuftherformed a protFctlve layfir 111 a thlckness 0f 4 phenoxyphenyl) 3stearoyl 5 pyrazolone as the magenta mrcrons. ThlS protective layer wasformed by adding coupler, an ultraviolet absorption layer containingCom- Slowly a 4% dlmethyl fofmamlde-wfltel Solution of 0116 pound 17,supra, as the ultraviolet absorbent, a red-sensiof the compoflnds 1714,Supra, as a g molecular W g tive emulsion layer containingN-n-octadecyl-1-hydroxy-4- fluorescent brlghtenlng agent Compound 24sulfo-Z-naphthamide as the cyan coupler, and a protective 25 mg the Pf9rmlllas as Shown below, well known layer, in this order, was preparedand designated 1 fluorescent bnghtenlng agent, to an aqueous gelatmsoluphotographic printing paper addition, a photo tron and applying theresulting mixture in a thickness of graphic color printing paper havingthe same photographic 5 lug/100 followed y y layers as above in the sameorder, but containing no ultra- The color photographic printing paperthus prepared violet absorbent in the intermediate layer between the wasdeveloped in a developer containing N-ethyl-N-B- green-sensitiveemulsion layer and the red-sensitive emulhydroxyethyl-p-phenylenediamineand thereafter subjected sion layer was prepared, and is designatedcolor phototo stop fixing, washing, bleach fixing, washing, hardening,graphic printing paper B. Compound 1 was incorporated washing, anddrying. The whiteness of the printing paper in each layer of thephotographic color printing paper A thus processed is shown in thefollowing table.

and photographic color printing paper B at a level of 5 mg./ 100 cm, andthe thus prepared color photographic DENSITY OF YELLOW COMIII"I(C))IENTOF UNEXPOSED POR- processing. The whiteness of the color photographicprinting papers thus processed is shown in the following table, in whichthe whiteness is shown by photographic density fluorescent Compoundbrightening of the yellow component 1n the unexposed portions of theagent 15 16 17 18 19 20 processed printing papers.

&

DENSITY or YELLOW COMPONENT IN UNEXPOSED POR- 3:8,; 218% 3:8; 33; 3:8;TION 8'88 8'88 8'83 8'88 883 8'8? 8? 83 0. 0. Printing Paper 0. 06 0.060.07 0.06 0.07 0.07 0.07 0.07 Layertowhichcomvoundisadded A B 8:88 8:888:8? 8:88 8:8? 8:83 883 8:83 0.06 0.06 0.07 0.06 0.07 0.07 0.07 0.07 ggg g g-gg 0.06 0. 06 0. 07 0.06 0.07 0.07 0.07 0.07 Y 0.06 0.06 0.07 0.060.07 0.07 0.07 0.07 Ultravioletabsorbinglayer(ormtermed1ate1ayer) 0 100.08 0.06 Q06 0'07 0'06 (107 0.07 Q07 0.07

8-83 0.06 0.06 0.07 0.06 0. 07 0.07 0.07 0.07 yanowela M Y 0.06 0. 060.07 0.06 0.07 0. 07 0. 07 0.07 Ba v dog 0.06 0.06 0.07 0.06 0.07 0.070.07 0.07 g z 0.11 0.11 0.12 0.11 0.12 0.12 0.12 0.12 e 0.11 0.11 0.120.11 0.12 0.12 0.12 0.12 0.12 0.12 0.13 0.12 0.13 0.13 0.13 0.13

From the above results, it can be seen that the effect of thefluorescent brightening agent was most remarkable when it wasincorporated in the uppermost layer, and that As can be clearly seenfrom the above results, when a the eifect became less as it wasincorporated in those high molecular fluorescent brightening agent ofthis inlayers nearer the support. Also, it should be noted that, ventionwas incorporated in the uppermost layer of the when the high-molecularweight fluorescent brightening color photographic printing paper, a veryremarkable Ra Ra N N X-- TN CH=CH N( l N N 5503M sonu N l R1 R1 and NX-- I N R I o N N N SOaM SOaM I I R1 R1 wherein 1R and R are each amember selected from the group consisting of a hydrogen atom, an alkylgroup having 1-8 carbon atoms, an aryl group having '6-12 carbon atoms,a hydroxyalkyl group having 2-4 carbon atoms, a substituted hydroxyalkyl group having 2-4 carbon atoms, a sulfoalkyl group having 1-4carbon atoms, and alkali metal salts and ammonium salts thereof; R is amember selected from the group consisting of a halogen atom, 0R, S

and

wherein R and R are each a member selected from the group consisting ofa hydrogen atom, an alkyl group having 1-12 carbon atoms, a hydroxyalkylgroup having 1-12 carbon atoms, a sulfoalkyl group, an alkali metal saltof said sulfoalkyl group, an ammonium salt of said sulfoal kyl group, acarboxyalkyl group, an alkali metal salt of said carboxyalkyl group, anammonium salt of said carboxyalkyl group, an alkyl group, an aryl grouphaving 6-18 carbon atoms, a hydroxyl derivative of said aryl group, acarboxyl derivative of said aryl group, a sulfonic acid derivative ofsaid aryl group, an alkali metal salt of each said derivative, anammonium salt of such said derivative, a cycloalkyl group havingZ-IOcarbon 1 35 atoms, and a substituted cycloalkyl group; A is a memberselected from the group consisting of an alkylene group having 4-5carbon atoms, an alkylene group containing a heterocyclic atom, and analkylene group containing a heterocyclic atomic group; Y is a memberselected from the group consisting of an alkylene group having 2-10carbon atoms, a substituted alkylene group having 2-1() carbon atoms, anallylene group having 6-18 carbon atoms and a substituted allylene grouphaving 6-18 carbon atoms, Z is a member selected from the groupconsisting of a divalent heterocyclic atom and a divalent heterocyclicatomic group; M is a member selected from the group consisting of analkali metal atom and NIL; X is a member selected from the groupconsisting of hydroxyl, chloro and amino; m is O or 1, and n is 5 to120.

2. The color photographic printing paper as claimed in claim 1 whereinsaid ultraviolet absorbent is a member selected from the groupconsisting of a benzotriazole, a benozophenone and a thiazolidone.

3. The color photographic printing paper as recited in claim 2 whereinthe amount of said compound is 05-10 mg./ cm. and the amount of saidultraviolet absorbent is 2-20 mg./ 100 cm.

4. The color photographic printing paper as recited in claim 1 whereinsaid printing paper comprises a layer containing said ultravioletabsorbent and a layer containing said compound, the layer containingsaid ultraviolet absorbent being positioned between saidcompound-containing layer and said support paper.

5. The color photographic printing paper as recited in claim 4, whereinsaid compound is incorporated in the uppermost protective layer of theprinting paper.

6. The color photographic printing paper as recited in claim 1 whereinsaid ultraviolet absorbent and said compound are both present in asingle layer.

7. The color photographic printing paper as recited in claim 1 whereinsaid ultraviolet absorbent is incorporated in a layer below theuppermost layer.

8. The color photographic paper as recited in claim 6 wherein saidultraviolet absorbent and said compound are present in a layer beneaththe uppermost layer.

9. The color photographic printing paper as claimed in claim 1 whereinsaid compound is selected from the group consisting of S0 Na SOaNa S ONa S 0 1%.

NORMAN G. TORCHIN, Primary Examiner E. C. KIMLIN, Assistant Examiner US.Cl. X.R. 96-48

